Patent GB-788834-A (GB)
Title: Improvements in inhibitors of ozone degradation of natural or synthetic rubber
IPC: C07F7/22
Filed: 1956-03-05
Abstract: A composition comprises a synthetic rubber e.g butadiene-styrene and butadiene-acrylonitrile copolymers, and as antiozonant an amine and an organotin compound of the formula RnSnQ, where R is a substituted or unsubstituted alkyl, aryl, aralkyl, or alkaryl radical, n is 1, 2 or 3, and Q is ­ (XXH) when n is 1, = X when n is 2, and - X Sn Rn when n is 3, X being oxygen, sulphur, selenium or tellurium, the groups X and R being bonded to tin, and when n is greater than 1 the R's may be the same or different.  The composition may contain 0.045 to 5 per cent of organo-tin compound and 0.03 to 2.5 per cent of amine.  The organo-tin compounds specified include phenyl, methyl, butyl and benzyl stannoic acid, di- and tri-phenyltin, di- and tri-methyltin, and di- and tri-butyltin sulphides, selenides, oxides and tellurides, metjyl diseleno-, phenylditelluro and butyldithio stannoic acids.  The amine may be selected from N,N1-dialkyl (or aryl) p-phenylenediamines, bis-alkyl (or aryl) polyalkylenediamines, alkyl or aryl naphthylamines, alkyl arylamines, and diarylamines, e.g. N,N1-dibutyl (or diphenyl or dioctyl or dinaphthyl) p-phenylene diamine, phenyl a  or phenyl b  naphthylamine, di-p-methoxy diphenylamine, 6 ethoxy-1,2, - dihydro - 2,2,4 - trimethylquinoline, and 1,2-dihydro 2,24-trimethyl-6-phenyl quinoline.  Examples are described illustrating the resistance to deterioration by ozone of compositions containing GRS synthetic rubber and N,N1-disec.butyl, p-phenylene diamine and (a) dibutyltin sulphide; (b) polymerized 1,2-dihydro 2,2,4-trimethyl quinoline and dibutyltin sulphide; (c) the ingredients of (b) and phenyl b -naphthylamine; (d) dibutyltin sulphide and petroleum hydrocarbon wax and (e) diphenyltin sulphide, respectively, and of compositions containing (a) N,N1-dioctyl-p-phenylene diamine and dibutyltin or dimethyltin sulphide, and (b) diphenyl propylene diamine and dibutyltin sulphide, respectively.  U.S.A. Specification 2,476,601 is referred to.ALSO:A natural or synthetic rubber composition includes as an antiozonant an amine and an organotin compound of the formula RnSnQ, where R is a substituted or unsubstituted alkyl, aryl, aralkyl, or alkaryl radical, n is 1, 2 or 3, and Q is ­ (XXH) when n is 1, = X when n is 2, and -X Sn Rn when n is 3, X being oxygen, sulphur, selenium or tellurium, the groups X and R being bonded to tin, and when n is greater than 1 the R's may be the same or different.  The composition may contain 0,045 to 5, and preferably 0,3 to 0,6 per cent by weight of organo-tin compound and 0,03 to 2,5, and preferably 0,2 to 0,3, per cent by weight of amine.  The organo-tin compounds specified include phenyl, methyl, butyl, and benzyl stannoic acid, di- and tri-phenyltin, di- and tri-methyltin, and di- and tri-butyltin sulphides, selenides, oxides, and tellurides, methyl diselenophenylditelluro, and butyldithio stannoic acids.  The amine may be selected from N, N1 dialkyl (or aryl) p-phenylenediamines, bis-alkyl (or aryl) polyalkylenediamines, alkyl or aryl naphthylamines, alkyl arylamines, and diarylamines, e.g., N, N1 dibutyl (or diphenyl or dioctyl or dinaphthyl) p-phenylene diamine, phenyl a  or phenylb naphthylamine, di-p-methoxy diphenylamine, 6 ethoxy-1, 2-dihydro-2, 2, 4-trimethylquinoline, and 1, 2 dihydro 2, 2, 4-trimethyl-6-phenyl quinoline.  Compositions of natural rubber, butadiene-styrene, and butadiene-acrylonitrile are referred to. Examples are described illustrating the resistance to deterioration by ozone of compositions containing natural rubber or GRS synthetic rubber and N, N1 di-sec. butyl, p-phenylene diamine and (a) dibutyltin sulphide (b) polymerized 1, 2 dihydro 2, 2, 4 trimethyl quinoline and dibutyltin sulphide (c) the ingredients of (b) and phenyl b  naphthylamine (d) dibutyltin sulphide and petroleum hydrocarbon wax and (e) diphenyltin sulphide, respectively, and of compositions containing (a) N, N1 dioctyl-p-phenylene diamine and dibutyltin or dimethyltin sulphide, and (b) diphenyl propylene diamine and dibutyltin sulphide, respectively.  U.S.A. Specification 2,476,661 is referred to.